Article
Chemistry, Organic
Hui Liu, Yingkun Yan, Min Li, Xiaomei Zhang
Summary: By utilizing chiral phosphoric acid as a catalyst, enantioselective aza-Friedel-Crafts reaction between 5-aminoisoxazoles and isatin-derived N-Boc ketimines was achieved, yielding novel 3-isoxazole 3-amino-oxindoles with high yields and moderate to good enantioselectivities. One product's absolute configuration was determined by X-ray crystal structural analysis, and a plausible reaction mechanism was proposed, followed by a successful scale-up reaction. Additionally, the product underwent Suzuki-Miyaura coupling with phenylboronic acid, resulting in moderate yield without affecting the enantioselectivity.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Applied
Huimiao Zhang, Patrick H. Toy
Summary: A halogen bond donor based on a 2,2'-bipyridine framework has been synthesized and used to catalyze Friedel-Crafts reactions of furans, yielding good reaction yields with moderate catalyst loading at low temperatures. The catalyst design allows for the potential development of an enantioselective version for stereo-selective catalysis.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Mohd Jubair Aalam, Deepa, Surendra Singh
Summary: In this study, imidazolium ionic liquids containing second-generation MacMillan catalysts were synthesized and used as organocatalysts for enantioselective Friedel-Crafts reaction. The results showed that the organocatalyst exhibited good catalytic activity and enantioselectivity towards different substrates and substituents under suitable reaction conditions. However, a decrease in catalytic activity and enantioselectivity was observed with increasing reaction cycles.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Junwei Zhang, Hao Wu, Weixin Zhang, Liming Wang, Ying Jin
Summary: A series of cinchona alkaloid silyl ether derivatives have been successfully used as catalysts for the enantioselective Friedel-Crafts reaction between indoles and isatins, yielding 3-hydroxy-2-oxindoles with high yields (78% to 96%) and excellent enantioselectivities (up to 99% ee). This methodology has broadened the catalyst type and substrate scope.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Zhengshuai Xu, Chaoren Shen, Hongru Zhang, Peng Wang, Kaiwu Dong
Summary: This research achieved the construction of chiral aza-quaternary carbon centers via C-N bond formation, providing chiral dihydroquinolinone derivatives with moderate to high yield and improved enantiomeric ratio. The use of a syringe pump to add o-iodoaniline was crucial in reducing side reactions and improving chemoselectivity. By utilizing the chirality induction of an assembled aza-quaternary stereogenic center, molecules with vicinal chiral quaternary carbon centers or multiple chiral centers can be rapidly prepared.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Danijel Glavac, Matija Gredicak
Summary: This study describes the synthesis of enantioenriched Betti base precursors containing a congested quaternary stereocenter. In a chiral phosphoric acid-catalyzed reaction, a series of in situ generated isoindolinone-derived ketimines and phenol derivatives yield products with good to excellent yields and moderate enantioselectivities. Conversion of the obtained products into chiral Betti bases while retaining optical purity is demonstrated.
NEW JOURNAL OF CHEMISTRY
(2022)
Review
Chemistry, Organic
Anup Biswas
Summary: The aza-Friedel-Crafts reaction allows for the efficient coupling of electron-rich aromatic systems with imines, facilitating the incorporation of aminoalkyl groups into the aromatic ring. This reaction offers a wide range of forming aza-stereocenters, which can be controlled by different asymmetric catalysts. This review highlights recent advances in asymmetric aza-Friedel-Crafts reactions mediated by organocatalysts and provides mechanistic insights into the origin of stereoselectivity.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Amjad Ali, Raveena Jajoria, Harish K. Harit, Ravi P. Singh
Summary: In this study, the addition of alpha-ketoamide top-quinone methide initiated by dialkylphosphite in the presence of organic base DBU was explored. The coupling of dialkylphosphites to alpha-ketoamides followed[1,2]-phospha-Brook rearrangement, generating alpha-phosphonyloxy enolates that were subsequently seized by p-quinonemethides. This two-step one-pot 1,6-conjugate addition method provides effective access to a series of isatin-incorporated phosphate-bearing 1,6-adducts with high yield and selectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Xuesuo Ma, Jiaxi Xu, Jingjing Liu, Jun He, Tong Chang, Qingbiao Yang, Ning Li, Dong Qian, Zhenjiang Li
Summary: H-bonding has achieved significant progress by utilizing an H-bond donor (HBD) and an H-bond acceptor (HBA). This study introduces a new type of organic ion pair that exhibits cooperative catalytic effects. A new mechanism of H-bonding catalysis is proposed.
Article
Chemistry, Applied
You-Song Cheng, Shih-Hsien Chan, Gunda Ananda Rao, Ramani Gurubrahamam, Kwunmin Chen
Summary: An asymmetric organocatalytic aza-Friedel-Crafts reaction was developed to synthesize enantioenriched Delta(4)-isoxazoline scaffold with a quaternary-substituted stereogenic center in good-to-excellent yields and enantioselectivity. This protocol involves the in situ generation of isoxazolium ions in the presence of a chiral phosphoric acid followed by heteroarene addition through asymmetric counteranion-directed catalysis.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Xi Xiao, Xiaobiao Lu, Ming Zhang, Haoqing Hou, Changfeng Wan, Jinbiao Liu
Summary: A novel synthetic method was successfully developed for the preparation of multisubstituted dihydrochromeno[2,3-b]indole derivatives in moderate to high yields using a catalytic environmentally benign iron salt.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Biochemistry & Molecular Biology
Zhe Chen, Liming Wang, Wenqin Tian, Ying Jin, Xin Qin
Summary: Takemoto's catalysts were used for the enantioselective Friedel-Crafts reaction, resulting in the synthesis of 3-aryl-3-hydroxyl-2-oxindoles with high yields (85-96%) and up to 99% ee. This methodology offers expanded substrate scope compared to previous examples catalyzed by cinchonidine thiourea.
MOLECULAR DIVERSITY
(2023)
Article
Chemistry, Multidisciplinary
Robert Li-Yuan Bao, Lei Shi, Kang Fu
Summary: A novel class of chiral spiro-fused bisoxazoline ligands with a deep chiral pocket was synthesized and successfully applied in a highly enantioselective chemical reaction. The reaction produced compounds with a trifluoromethylated all-carbon quaternary stereocenter, showing good yields and enantioselectivities.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Inorganic & Nuclear
Amir Yeganeh-Salman, Iris Elser, Karlee L. Bamford, Daniel Ebanks, Douglas W. Stephan
Summary: In this study, a catalytic conversion of B-X to B-H bond was achieved using a small amount of [Ph3C](+) as an initiator with Et3SiH. This method was successfully applied to six haloboranes. Additionally, C-F bond activation of benzyl fluorides was observed in the presence of arenes, leading to the formation of Friedel-Crafts products using B-H-9-BBN in the presence of Et3SiH. The protocol provides a simple, cost-effective, and mild route to 1,1-diarylmethanes from benzyl fluorides with high yields (up to 99%).
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Organic
Min Li, Yihua Chen, Yingkun Yan, Min Liu, Min Huang, Wenzhe Li, Lianyi Cao, Xiaomei Zhang
Summary: An enantioselective addition reaction catalyzed by a chiral phosphoric acid has been developed for the synthesis of quaternary alpha-isoxazole-alpha-alkynyl amino acid derivatives. The reaction showed high yields and good to excellent enantioselectivities, and the hydrogen-bonding interaction between the amino-isoxazole and chiral phosphoric acid played a vital role in the selectivity.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Zheng-Jia Shen, Chen Zhu, Xiao Zhang, Chao Yang, Magnus Rueping, Lin Guo, Wujiong Xia
Summary: This article describes a selective (deutero)hydrodefluorination reaction via electrolysis, which achieves remarkable chemoselectivity control by the addition of different organoboron sources. The method is operationally simple, scalable, and provides access to high-value building blocks for medicinal chemistry in one step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Jose J. Delgado-Marin, Alejandra Rendon-Patino, Vijay Kumar Velisoju, Gadde Sathish Kumar, Naydu Zambrano, Magnus Rueping, Jorge Gascon, Pedro Castano, Javier Narciso, Enrique V. Ramos-Fernandez
Summary: We demonstrate that ZIFs used as catalysts for CO2 insertion suffer from irreversible degradation by leaching, leading to decreased stability and catalytic activity. Additional treatments are necessary to improve their stability.
CHEMISTRY OF MATERIALS
(2023)
Article
Multidisciplinary Sciences
Long Huang, Marcin Szewczyk, Rajesh Kancherla, Bholanath Maity, Chen Zhu, Luigi Cavallo, Magnus Rueping
Summary: In this study, stereodivergent allylic C(sp(3))-H bond arylations were successfully developed through a systematic investigation of the direction and degree of stereoselectivity in the cross-coupling process. Unlike the typical photosensitized geometrical isomerization of alkenes, the catalytic reaction demonstrated the feasibility of switching the C-C double bond stereoselectivity through ligand control and steric and electronic effects.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Sharath Kandambeth, Vinayak S. Kale, Dong Fan, Jeremy A. A. Bau, Prashant M. M. Bhatt, Sheng Zhou, Aleksander Shkurenko, Magnus Rueping, Guillaume Maurin, Osama Shekhah, Mohamed Eddaoudi
Summary: This work reports an innovative strategy for the synthesis of chemically robust metal-organic frameworks (MOFs) and their application as catalysts for the electrocatalytic oxygen evolution reaction (OER). The study demonstrates that bimetallic MOF systems with regulated metal ratios exhibit excellent catalytic activity and structural stability for OER.
ADVANCED ENERGY MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Saidkhodzha Nematulloev, Arunachalam Sagadevan, Badriah Alamer, Aleksander Shkurenko, Renwu Huang, Jun Yin, Chunwei Dong, Peng Yuan, Khursand E. Yorov, Azimet A. Karluk, Wasim J. Mir, Bashir E. Hasanov, Mohamed Nejib Hedhili, Naveen M. Halappa, Mohamed Eddaoudi, Omar F. Mohammed, Magnus Rueping, Osman M. Bakr
Summary: This study reports the synthesis of atomically precise copper hydride nanoclusters with a controlled defect, which were demonstrated to be highly selective catalysts for C-C cross-couplings. The work highlights the potential of defective nanoclusters as model systems for investigating individual defects, correlating defects with physicochemical properties, and rationally designing new nanoparticle catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Haifeng Chen, Chen Zhu, Huifeng Yue, Magnus Rueping
Summary: In this study, a nickel-catalyzed, three-component reductive protocol for group 14 element hetero-difunctionalization of 1,3-enynes using electrochemistry is described. The method is mild, selective, and general, allowing for the silyl-, germanyl-, and stannyl-alkylation of enynes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Serik Zhumagazy, Chen Zhu, Huifeng Yue, Magnus Rueping
Summary: This article describes a nickel-catalyzed C-Se cross-coupling reaction between aryl iodides and selenols. The newly developed catalytic methodology provides easy access to various asymmetric selenium-containing compounds. The reaction exhibits excellent functional group tolerance, a wide range of substrates, high efficiency, and operates under mild conditions. Importantly, the protocol can be readily scaled up to gram-scale reactions without a loss of yield.
Article
Multidisciplinary Sciences
Liuzhuang Xing, Qian Yang, Chen Zhu, Yilian Bai, Yurong Tang, Magnus Rueping, Yunfei Cai
Summary: In this study, the authors successfully incorporated privileged homogeneous bipyridyl-based Ni-catalysts into highly ordered and crystalline potassium poly(heptazine imide) (K-PHI), achieving the development goal of heterogeneous metallaphotocatalysis. The LnNi-PHI catalysts exhibit superior chemical stability and recyclability in C-P, C-S, C-O and C-N cross-coupling reactions.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Gadde Sathish Kumar, Chen Zhu, Rajesh Kancherla, Prashant S. S. Shinde, Magnus Rueping
Summary: An efficient method for the reductive cross-electrophile coupling of aziridines with aryl halides using nickel electrocatalysis is reported. Valuable phenethylamines are synthesized at room temperature in good yields. The reaction is distinct from conventional and photochemical couplings, and the role of Ni(II) organometallic complexes and electrodes in the reaction mechanism are examined.
Review
Chemistry, Physical
Sam Mathew, Dominik Renn, Magnus Rueping
Summary: Amine transaminases play a crucial role in the synthesis of chiral amines, which are essential building blocks in pharmaceuticals and fine chemicals. Advances in enzyme discovery, process engineering, and protein engineering have significantly enhanced the use of transaminases in organic synthesis. Enzymatic cascade engineering has emerged as an efficient and environmentally friendly approach for chiral amine synthesis, allowing the generation of valuable products from inexpensive starting materials. This review focuses on the utilization of amine transaminases in enzymatic and chemoenzymatic cascades for chiral amine synthesis.
Article
Chemistry, Physical
Haifeng Chen, Chen Zhu, Huifeng Yue, Magnus Rueping
Summary: An efficient cobalt-catalyzed carbon-germanium bond formation method has been developed, providing access to a wide range of functionalized germane-containing compounds. This method shows a broad scope and good tolerance toward various functional groups, and is conducted under mild reaction conditions. Mechanistic studies shed light on the unexpected reaction pathway and sequential activation of different electrophiles.
Article
Biotechnology & Applied Microbiology
Ram Karan, Dominik Renn, Shuho Nozue, Lingyun Zhao, Satoshi Habuchi, Thorsten Allers, Magnus Rueping
Summary: This study presents a genetic engineering and chemical modification approach to functionalize the major gas vesicle nanoparticle (GVNP) protein, GvpA. By introducing combinatorial cysteine mutagenesis within GvpA and expanding the N- and C-terminal regions, GvpA single, double, and triple cysteine variant libraries were generated. Thiol-maleimide chemistry was used to introduce biotechnologically relevant activities to the GVNPs. This approach significantly expands the bioengineering and functionalization potential of these novel protein nanomaterials.
JOURNAL OF NANOBIOTECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Wenhuan Huang, Chenyang Su, Chen Zhu, Tingting Bo, Shouwei Zuo, Wei Zhou, Yuanfu Ren, Yanan Zhang, Jing Zhang, Magnus Rueping, Huabin Zhang
Summary: The solar-driven evolution of hydrogen from water using particulate photocatalysts is a promising method for achieving a stable supply of renewable energy. However, the efficiency of photocatalytic water splitting is low due to sluggish electron-hole pair separation kinetics. In this study, highly oxidized Mo species incorporated into Cd0.5Zn0.5S nanorods exhibit significantly enhanced photocatalytic efficiency through inhibited electron-hole recombination.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Editorial Material
Multidisciplinary Sciences
Huifeng Yue, Chen Zhu, Magnus Rueping
Review
Chemistry, Multidisciplinary
Jingchang Zhang, Magnus Rueping
Summary: In recent years, the combination of photocatalytic hydrogen atom transfer (HAT) and transition metal catalysis has become an important strategy for the synthesis of C(sp(3))-carbon and C(sp(3))-hetero bonds. This approach has been widely used in organic synthesis, leading to new transformations. This review summarizes the recent advances in sp(3) C-H functionalizations through photocatalytic HAT followed by transition metal catalysis, focusing on the diverse strategies, synthetic applications, and detailed mechanisms involved in these reactions. The understanding of these mechanisms is crucial for the rational design of new catalysts and reaction conditions to improve the efficiency of these transformations. We hope that this review will serve as a valuable resource for researchers in the field of metallaphotoredox catalysis and inspire further development in green chemistry, drug synthesis, material science, and other related fields.
CHEMICAL SOCIETY REVIEWS
(2023)
